Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/04—Ingredients treated with organic substances
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
  • C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2991—Coated
  • Y10T428/2998—Coated including synthetic resin or polymer

Definitions

• the present invention relates to a method of fixing or "grafting" polymerized substances to the surface of inorganic particles of a filler material in order to obtain economically filler materials that are easier to use in miscellaneous industries such as the rubber, plastic or paints industries, while imparting improved properties to the finished products.
• This method comprises the steps of:
• the surface-active agent or surfactant and its reagent may be selected from a wide range of substances, provided only that they lend themselves to condensation or polymerization reactions.
• the method of this invention comprises the steps of:
• an aminoplast-type polymer is caused to adhere to the crystallites in a physico-chemical and indestructible manner when the grafted filler material is subsequently introduced into an organic binder, whereby this binder will react with this grafted filler material as it would with an organic substance.
• the thus grafted filler materials are particularly suited for use in the rubber industry due to the presence of aminated products participating in the vulcanization.
• non-ionic, hydroxylated or polyethoxylated surfactants such as ethylene glycol, glycerol, polyethylene glycols, glycol ethers for the aminated cationic surfactants.
• Reagents consisting of diacids and corresponding to these surfactants, so as to form polyesters may be selected for example from the group of diacids currently used in the manufacture of polyester, such as:
• the filler materials adapted to be treated by this grafting method may be of natural or synthetic type:
• silicious fillers quartz, colloidal silica, kieselguhr, etc . . . ;
• silicated fillers chalk, calcium carbonate, dolomite, marmor, etc . . . ;
• sulfated fillers baryte, gypsum, etc . . .
• the surfactant having aminated functions and of which the molecule has one end of its chain strongly fixed to the filler material and capable of preserving free and available --NH-- active radicals may be:
• a cationic surfactant such as N-alkyl-amino-alkylamines, that is, di-amines of the R -- NH -- R' -- NH 2 type, wherein R is a chain comprising 4 to 24 carbon atoms and R' a chain comprising at the most 6 carbon atoms, said di-amines adhering easily through their -- NH 2 function to the silicated and sulfated minerals;
• an amphoteric surfactant of the amino-acid type for instance N-- alkyl - amino - alkyl carboxylic acids: R -- NH -- R' -- COOH, wherein R and R' are hydrocarbon chains of the same type as in the products recited in the above paragraph (1) and wherein the -- COOH function will form a satisfactory compound with carbonated minerals;
• a polyethoxylated surfactant such as N - alkyl-aminoalkylamines, i.e., oxyethylenated di-amines of the type: ##STR1## adhering to low chemical reactivity minerals by at least one of their (CH 2 -- CH 2 -- O) functions, wherein p, q, r are integers in the range of 3 to 12.
• aminated functions of these three types of surfactants may of course be multiplied linearly in order to dispose of a greater number of free and available -- NH -- functions for subsequent reactions.
• the quantity of surfactants having aminated functions may vary from 0.5 to 50% by weight in relation to the filler material.
• the percentage of surfactants lies preferably in the range from 0.5 to 10%.
• a higher percentage of surfactant may be used with a filler material capable of absorbing organic products, such as attapulgite, montmorillonite, silica gel, and sepiolite.
• the surface treatment of the filler material with said surfactant or surfactants is easily achieved by mixing, crushing or triturating the two component substances in the cold state or in a heated state.
• the aldehydic-function product capable of reacting in the fashion of aminoplasts on the free and available -- NH-- functions of the surfactant adhering to the filler material may be:
• R--CHO form such as formal, acetaldehyde, propionaldehyde, furfural, wherein R is a saturated or cyclic hydrocarbon radical
• R'CHO form such as acrylic aldehyde, crotonaldehyde, wherein R' is a hydrocarbon comprising one or a plurality of ethylene linkages
• a di-aldehydic product such as glyoxal.
• the quantity of aldehydic function reagent to be used is subordinate to the quantity of aminated function surfactant used for treating the filler material; however, 1.5 to 2.5 times the stoichiometric amount are necessary, which as a rule is equivalent to the addition of 0.3 to 30% of reagent in relation to the weight of filler material.
• the reaction between the aldehydic-function product, dissolved or not in water, and the filler material treated with the surfactant having aminated functions, is accomplished in the heated state (100° C. or more), for example in a Grignard reactor.
• the reactor time is about one hour but depends on temperature.
• the water resulting from the condensation developing between the aldehydic function product and the surfactant, and also the water introduced for dissolving the reagent, are then discharged by reversing the cooler of the Grignard reactor and possibly by applying vacuum thereto.
• a polymer of the aminoplast can be grafted to the filler material.
• the grafted polymer has the form: ##STR2##
• Radical R and R' are derived from the surfactant and radicals R" from the aldehydic-function reagent.
• a mixture is prepared in the heated state which comprises:
• the thus treated kaolinite filler material is then introduced into a Grignard reactor with 13% of an aqueous 30-percent formal solution.
• the dry product is extracted and reduced to a fine powder, and the grafted filler material thus obtained is tested at 60% and 120% in a conventional natural rubber formula in comparison with Argirec B-24.
• the tensile strength is improved by at least 13 percent
• the A-Shore hardness number is improved by 3 to 4, and
• the tearing strength is improved considerably: 26 to 45 percent.
• the kaolinic filler material obtained as disclosed in Example 1 is treated with 5% of DINORAM S and introduced into a GRIGNARD reactor with 13% by weight of an aqueous solution containing 30% formal and 0.5% resorcinol.
• the tensile strength is increased by at least 20%;
• the A-Shore hardness number is increased by 5 to 6;
• the tearing strength is increased very considerably: 50 to 75%.
• the physico-chemical bonds between the organic binders and the grafted filler material according to this method are therefore considerably stronger than those tested when using untreated filler materials or filler materials treated with organic products and/or inorganic salts in order to modify only their surface physico-chemical properties.
• the fillers used are the same as those mentioned hereinabove.
• fillers are treated at temperatures within the range of 110° to 150° C., i.e. with a view to remove the maximum quantity of excess water (--OH--H--OH--H--OH) and to substitute a surface-active layer (--OH--H--OH--R) therefor when the product is dried completely and the surfactant is added, this addition being accomplished in a quantity proportional to the specific surface area and to the active points of the filler, and may range from about 0.5% to about 10% by weight of treated filler material.
• Acid anhydride may then be added to the thus coated filler for producing the chain reaction with the free hydroxyl functions.
• anhydride depends on the specific nature and quantity of the surfactants and may therefore range from 1 to 20%
• the temperature, time and vaccum should be adjusted with a view to obtain the maximum yield from each condensation, esterification and polymerization reaction.
• the temperatures should be in the range of 110° to 150° C.
• the reaction time in the range of 15 mn to 2 hours
• the vacuum may be necessary for eliminating any water likely to be released during the reactions.
• a natural filler material such as talc finely ground so that no particle thereof has a size greater than 50 ⁇ (Standard talc OOS produced by the French Company "Societe des Talcs de Luzenac”) is introduced into a powerful mixer of which the double wall is so heated that the talc temperature becomes stabilized at 130° C. after 15 mn of stirring so as to remove any surface water therefrom, as well as its residual and humidity water.
• glycerol 3% by weight are added to the mixture and the latter is stirred during 15 to 30 mn at the same temperature to obtain the maximum homogeneity and physico-chemical bond between talc and glycerol.
• the grafted filler wherein the talc is grafted by means of a glycerol polymaleate, is thus ready for use in plastic materials for example at the rate of 40 parts of filler for 60 parts of polypropylene.
• a natural filler material such as chalk free of any particle greater than 12 ⁇ , (e.g. "Micronic-O" produced by the French Company: Societe des Blancs Mineraux, Paris) is introduced into a mixer having its double wall heated to stabilize the chalk temperature at 130° C. after 15 minutes of energic stirring, so as to free it from any humidity water, surface water and residual water.
• phthalic anydride 1.5% may then be added gradually while stirring strongly at 130° C. during 15 mn.
• the grafted filler i.e., chalk grafted by a polyphthalate
• plastic materials such as 100% P.V.C. with 50% of octyl phthalate as a plastifier.
• the grafted filler is particularly advantageous, due to the improvement of all its properties, especially resistivity, which makes this product particularly adequate for manufacturing electric cables.
• these products may be used as filler materials in all industries utilizing as basic materials elastomers or plastomers, i.e., the rubber, plastic, paints, glue industries, etc . . . , in that they facilitate the dispersion while imparting improved mechanical properties to the finished products and articles.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Graft Or Block Polymers (AREA)
• Processes Of Treating Macromolecular Substances (AREA)

Applications Claiming Priority (4)

Related Child Applications (1)

Publications (1)

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Family Applications (1)

Country Status (9)

Cited By (12)

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Citations (9)

• 1976
  • 1976-03-08 FR FR7606508A patent/FR2343780A2/fr active Granted
  • 1976-03-23 GB GB11702/76A patent/GB1540288A/en not_active Expired
  • 1976-03-23 BR BR7601757A patent/BR7601757A/pt unknown
  • 1976-03-24 ES ES446331A patent/ES446331A1/es not_active Expired
  • 1976-03-25 DE DE19762612746 patent/DE2612746A1/de not_active Withdrawn
  • 1976-03-26 US US05/670,557 patent/US4129549A/en not_active Expired - Lifetime
  • 1976-03-26 IT IT21623/76A patent/IT1063250B/it active
  • 1976-03-26 NO NO761066A patent/NO761066L/no unknown
  • 1976-03-27 JP JP51033114A patent/JPS51142044A/ja active Pending

Patent Citations (9)

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